Correlation between Al2O3 particles and interface of Al-Al2O3 coatings by cold spray

Al-Al₂O₃ composite coatings with different Al₂O₃ particle shapes were prepared on Si and Al substrate by cold spray. The powder compositions of metal (Al) and ceramic (Al₂O₃) having different sizes and agglomerations were varied into ratios of 10:1 wt% and 1:1 wt%. Al₂O₃ particles were successfully incorporated into the soft metal matrix of Al. It was found that crater formation between the coatings and substrate, which is typical characteristic signature of cold spray could be affected by initial starting Al₂O₃ particles. In addition, when the large hard particles of fused Al₂O₃ were employed, the deep and big craters were generated at the interface between coatings and hard substrates. In the case of pure soft metal coating such as Al on hard substrate, it is very hard to get proper adhesion due to lack of crater formation. Therefore, the composite coating would have certain advantages.     

Charge trapping at Pt/high-k dielectric (Ta2O5) interface

A detailed analysis of the effects of constant low current injection was done, both in accumulation (J=0.001-0.2 mA cm⁻²) and in inversion (J=0.001-0.04 mA/cm²). The samples under investigation were metal-insulator-silicon structures containing high-k dielectric Ta₂O₅ radio frequency sputtered on p-type Si wafers, with Pt metal gate electrodes. The obtained results were compared with the ones obtained for Al gate samples. This experiment confirms the occurrence of charge trapping in the case of high-work-function Pt as metal. The effect has been attributed to emitting of electrons into the Pt conduction band during which creation of empty traps in the dielectric occurs, which then attract electrons injected in the dielectric. In order to examine the reversibility of the process, successive short runs as well as long runs (up to 10000 s) were performed.     

Binding energies of elements at the interface between oxygen-ion-irradiated ZrO2–Y2O3 films and an iron substrate

Binding energies of elements at the interface of oxygen-ion-irradiated ZrO₂–Y₂O₃ films on an iron substrate were investigated by using X-ray photoelectron spectroscopy (XPS) combined with ion etching. In addition to Zr or Fe simple binary suboxides, it is found that some Zr–O–Fe-like bonding configuration is formed due to ion irradiation, which has a favorable effect on the adhesion of the film to the substrate.     

Preparation and properties of composite ceramic coating containing Al2O3–ZrO2–Y2O3 on AZ91D magnesium alloy by plasma electrolytic oxidation

A composite ceramic coating containing Al₂O₃–ZrO₂–Y₂O₃ was successfully prepared on AZ91D magnesium alloy by plasma electrolytic oxidation (PEO) technique in an alkaline aluminate electrolyte. The morphology, elemental and phase composition, corrosion behavior and thermal stability of the uncoated and coated samples were studied by environmental scanning electron microscopy (ESEM), energy dispersive X-ray spectrometer (EDS), X-ray diffractometer (XRD), electrochemical corrosion test, high temperature oxidation test and thermal shock test. The results showed that the composite ceramic coating was composed of Al₂O₃, c-ZrO₂, t-ZrO₂, Y₂O₃ and some magnesium compounds, such as MgO, MgF₂ and MgAl₂O₄. After PEO treatment, the corrosion potential of AZ91D alloy was increased and the corrosion current density was significantly reduced. Besides, the coated magnesium alloys also showed excellent high temperature oxidation resistance and thermal shock resistance at 500 °C environment.     

Molecular dynamics simulation comparison of atomic scale intermixing at the amorphous Al2O3/semiconductor interface for a-Al2O3/Ge, a-Al2O3/InGaAs, and a-Al2O3/InAlAs/InGaAs

The structural properties of a-Al₂O₃/Ge, a-Al₂O₃/In_0.5Ga_0.5As and a-Al₂O₃/In_0.5Al_0.5As/InGaAs interfaces were investigated by density-functional theory (DFT) molecular dynamics (MD) simulations. Realistic a-Al₂O₃ samples were generated using a hybrid classical-DFT MD “melt and quench” approach. The interfaces were formed by annealing at 700 K/800 K and 1100 K with subsequent cooling and relaxation. The a-Al₂O₃/Ge interface demonstrates pronounced interface intermixing and interface bonding exclusively through Al–O–Ge bonds generating high interface polarity. In contrast, the a-Al₂O₃/InGaAs interface has no intermixing, Al–As and O–In/Ga bonding, low interface polarity due to nearly compensating interface dipoles, and low substrate deformation. The a-Al₂O₃/InAlAs interface demonstrated mild intermixing with some substrate Al atoms being adsorbed into the oxide, mixed Al–As/O and O–Al/In bonding, medium interface polarity, and medium substrate deformation. The simulated results demonstrate strong correlation to experimental measurements and illustrate the role of weak bonding in generating an unpinned interface for metal oxide/semiconductor interfaces.     

Effect of BiFeO3 addition on Bi2O3–ZnO–Nb2O5 based ceramics

In this paper, low temperature sintering of the Bi₂(Zn_1/3Nb_2/3)₂O₇ (β-BZN) dielectric ceramics was studied with the use of BiFeO₃ as a sintering aid. The effects of BiFeO₃ contents and the sintering temperature on the phase structure, density and dielectric properties were investigated. The results showed that the sintering temperature could be decreased and the dielectric properties could be retained by the addition of BiFeO₃. The structure of BiFeO₃ doped β-BZN was still the monoclinic pyrochlore phase. The sintering temperature of BiFeO₃ doped β-BZN ceramics was reduced from 1000 °C to 920 °C. In the case of 0.15 wt.% BiFeO₃ addition, the β-BZN ceramics sintered at 920 °C exhibited good dielectric properties, which were listed as follows: ε_r = 79 and tan δ = 0.00086 at a frequency of 1 MHz. The obtained properties make this composition to be a good candidate for the LTCC application.     

Band bending at the Si(1 0 0)-Si3N4 interface studied by photoreflectance spectroscopy

Photoreflectance spectroscopy has been used to measure the band bending at the p-Si(1 0 0)-Si₃N₄ interface subjected to annealing and ion implantation. Upon annealing, unimplanted interfaces exhibit a constant band bending of about 0.77 eV, even though the spectral amplitude changes due to variations in the way minority carriers are annihilated at the interface. Implantation reduces the band banding, although subsequent annealing in stages up to 900 °C progressively restores the bending to its original value through pathways exhibiting a wide range of activation barriers.     

Composition of Ta2O5 stacked films on N2O- and NH3-nitrided Si

The composition and microstructure of rf sputtered 20 nm Ta₂O₅ on N₂O or NH₃ Rapid Thermal Nitrided (RTN) Si substrates have been investigated by X-ray photoelectron spectroscopy. RTN at 800 and 850 °C is effective to suppress active oxidation of Si. There is no evidence for the presence of SiO₂ at Si interface. A lightly nitrided surface is established in both cases without a formation of detectable oxynitride layer at Si. A layered nature of the films is observed, with stoichiometric tantalum pentoxide at and close to the films’ surface. In the depth, the films are mixed ones whose composition depends on the nitridation ambient. N₂O treatment stimulates oxidation processes during the film deposition while NH₃ nitridation results to a less effective oxidation and produces Ta-silicate like film. The correlation between the composition of the interfacial regions and the nitridation gas is also discussed. The results suggest that hydrogen, as a component of nitridation ambient, plays significant role in the reactions controlling the exact composition of the deposited Ta₂O₅, activating reactions with nitrogen. Nitrogen related reactions likely occur with NH₃ processing but do not with N₂O one. The presence of nitrogen feature is not detected in N₂O-samples spectra at all. In the integration perspective, preliminary RTN of Si in N₂O or NH₃ could be a suitable way to produce layered Ta₂O₅-based films with more or less presence of tantalum silicate with a trace of nitrogen, either only at the interface with Si (N₂O-process) or in the whole film (NH₃-process).     

Optical and electrical properties of binary WO3–Pb3O4 glasses

A glass system of the composition xWO₃+(100−x)Pb₃O₄, with x=5, 10, 20 and 30 mol.% was prepared. The optical absorption, ac and dc conductivities are the subject of the present work. The optical absorption indicates that the electronic transition is indirect and is associated with phonon assisted transition. The exponential dependence of the absorption coefficient as a function of the incident photon energy suggests that the Urbach rule is obeyed, and indicates the formation of a band tail. On the other hand, ac conductivity measurements are performed in the frequency range 0.1–100 kHz, and in the temperature range 300–600 K. The results of the electrical conductivity are discussed on the basis of electronic glass conduction models. Correlated narrow-band limit for random sites and single polaron hopping model are found to describe the experimental results effectively. The dielectric constant was correlated to the optical band gap and a satisfactory relation was found. It was also possible to calculate the thermochromic properties from independent ac and dc measurements, and it was possible to evaluate the optical gap at 0 K by extrapolation.     

Correlation among electronic polarizability, optical basicity and interaction parameter of Bi2O3–B2O3 glasses

For optical basicity and electronic polarizability, the previous studies basically concentrate on the wavelength range of the visible light region. However, heavy metal oxides glasses have a reputation of being good materials for infrared region. In this study, new data of the average electronic polarizability of the oxide ion _O^2-, optical basicity Λ and Yamashita–Kurosawa's interaction parameter A of Bi₂O₃–B₂O₃ glasses have been calculated in a wavelength range from 404.66 to 1083.03 nm. The present investigation suggests that both _O^2- and Λ increase gradually with increasing wave number, and A decreases with increasing wave number. Furthermore, close correlations are studied among _O^2-, Λ, A and refractive index n in this paper. Particularly, it has been found that a quantitative relationship between electronic polarizability and optical basicity is observed in a wavelength range from 404.66 to 1083.03 nm. Our present study extends over a wide range of _O^2-, Λ and A values.     

Nature of intrinsic luminescence in the glasses of CaO–Ga2O3–GeO2 system

The intrinsic luminescence of glasses of the CaO–Ga₂O₃–GeO₂ system has been investigated. High chemical purity and optical quality glasses, both undoped and doped with transition and rare-earth ions with different compositions, were obtained by high-temperature synthesis. The influences of the basic glass composition, impurities (Cr³⁺, Mn²⁺, Eu²⁺, Nd³⁺, Ho³⁺, Er³⁺, and Ce³⁺) and different kinds of excitation, on the intrinsic luminescence of the CaO–Ga₂O₃–GeO₂ glasses were investigated. The nature and possible mechanisms of the intrinsic luminescence in glasses of this system are discussed. The proposed models of intrinsic luminescence are supported by electron spin resonance spectroscopy.     

Sintering of glasses in the system RO–Al2O3–BaO–SiO2 (R=Ca, Mg, Zn) studied by hot-stage microscopy

Glass–ceramics for sealing solid oxide fuel cells (SOFCs) were developed by sintering and crystallization of the powdered glass seal. The non-isothermal sintering kinetics and crystallization kinetics were studied for four glasses in the system 50SiO₂·(45−x)BaO·xRO·5Al₂O₃ (R=Ca, Mg, Zn and x=0, 15) (mol%). Hot-stage microscopy (HSM) and differential thermal analysis (DTA) measurements demonstrated that it is possible to first sinter and then crystallize these glasses obtaining glass–ceramic seals with thermal expansion coefficients in the range 9–12×10⁻⁶ K⁻¹.

The non-isothermal sintering kinetics was analyzed by computer simulations using a previously reported model of sintering for polydispersed glass powders which takes into account the particle size distribution, surface energy and viscosity. Good agreement was found between the measured kinetics with HSM and the calculated kinetics for all glasses.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

Characterization of interface between CuInSe2 and In2O3

CuInSe₂/In₂O₃ structures were formed by depositing CuInSe₂ films by stepwise flash evaporation onto In₂O₃ films, which were grown by DC reactive sputtering of In target in presence of (Ar+O₂) gas mixture. Phase purity of the CuInSe₂ and In₂O₃ films was confirmed by Transmission Electron Microscopy (TEM) studies. X-ray diffraction (XRD) results on CuInSe₂/In₂O₃/glass structures showed sharp peaks corresponding to (112) plane of CuInSe₂ and (222) plane of In₂O_3. Rutherford Backscattering Spectrometry (RBS) investigations were carried out on CuInSe₂/In₂O₃/Si structures in order to characterize the interface between In₂O₃ and CuInSe₂. The results show that the CuInSe₂ films were near stoichoimetric and In₂O₃ films had oxygen deficient composition. CuInSe₂/In₂O₃ interface was found to include a ∼20 nm thick region consisting of copper, indium and oxygen. Also, the In₂O₃/Si interface showed the formation of ∼20 nm thick region consisting of silicon, indium and oxygen. The results are explained on the basis of diffusion/reaction taking place at the respective interfaces.     

High-k Al2O3 MOS structures with Si interface control layer formed on air-exposed GaAs and InGaAs wafers

This paper attempts to realize unpinned high-k insulator-semiconductor interfaces on air-exposed GaAs and In_0.53Ga_0.47As by using the Si interface control layer (Si ICL). Al₂O₃ was deposited by ex situ atomic layer deposition (ALD) as the high-k insulator. By applying an optimal chemical treatment using HF acid combined with subsequent thermal cleaning below 500 °C in UHV, interface bonding configurations similar to those by in situ UHV process were achieved both for GaAs and InGaAs after MBE growth of the Si ICL with no trace of residual native oxide components. As compared with the MIS structures without Si ICL, insertion of Si ICL improved the electrical interface quality, a great deal both for GaAs and InGaAs, reducing frequency dispersion of capacitance, hysteresis effects and interface state density (D_it). A minimum value of D_it of 2 × 10¹¹ eV⁻¹ cm⁻² was achieved both for GaAs and InGaAs. However, the range of bias-induced surface potential excursion within the band gap was different, making formation of electron layer by surface inversion possible in InGaAs, but not possible in GaAs. The difference was explained by the disorder induced gap state (DIGS) model.     

Hydroxylated α-Al2O3 (0 0 0 1) surfaces and metal/α-Al2O3 (0 0 0 1) interfaces

X-ray photoelectron spectroscopy was applied to study the hydroxylation of α-Al₂O₃ (0 0 0 1) surfaces and the stability of surface OH groups. The evolution of interfacial chemistry of the α-Al₂O₃ (0 0 0 1) surfaces and metal/α-Al₂O₃ (0 0 0 1) interfaces are well illustrated via modifications of the surface O1s spectra. Clean hydroxylated surfaces are obtained through water- and oxygen plasma treatment at room temperature. The surface OH groups of the hydroxylated surface are very sensitive to electron beam illumination, Ar⁺ sputtering, UHV heating, and adsorption of reactive metals. The transformation of a hydroxylated surface to an Al-terminated surface occurs by high temperature annealing or Al deposition.     

Experimental and theoretical studies of Si-CN bonds to eliminate interface states at Si/SiO2 interface

Cyanide treatment, which includes the immersion of Si in KCN solutions followed by a rinse, effectively passivates interface states at Si/SiO₂ interfaces by the reaction of CN⁻ ions with interface states to form Si-CN bonds. X-ray photoelectron spectroscopy (XPS) measurements show that the concentration of the CN species in the surface region after the cyanide treatment is ∼0.25 at.%. Take-off angle-dependent measurements of the XPS spectra indicate that the concentration of the CN species increases with the depth from the Si/SiO₂ interface at least up to ∼2 nm when ultrathin SiO₂ layers are formed at 450 °C after the cyanide treatment. When the cyanide treatment is applied to metal-oxide-semiconductor (MOS) solar cells with 〈ITO/SiO₂/n-Si〉 structure, the photovoltage greatly increases, leading to a high conversion efficiency of 16.2% in spite of the simple cell structure with no pn-junction. Si-CN bonds are not ruptured by air mass 1.5 100 mW cm⁻² irradiation for 1000 h, and consequently the solar cells show no degradation. Neither are Si-CN bonds broken by heat treatment at 800 °C performed after the cyanide treatment. The thermal and irradiation stability of the cyanide treatment is attributable to strong Si-CN bonds, whose bond energy is calculated to be 1 eV higher than that of the Si-H bond energy using a density functional method.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Cluster size effects on hydrazine decomposition on Irn/Al2O3/NiAl(1 1 0)

A series of planar model catalysts were prepared by deposition of size-selected on Al₂O₃/NiAl(1 1 0), and hydrazine decomposition chemistry was used to probe their size-dependent chemical properties. Small Ir_n (n ? 15) on Al₂O₃/NiAl(1 1 0) are able to induce hydrazine decomposition at temperatures well below room temperature, with significant activity first appearing at Ir₇. Both activity and product branching are strongly dependent on deposited cluster size, with these small clusters supporting only the simplest decomposition mechanism: dehydrogenation and N₂ desorption at low temperatures, followed by H₂ recombinative desorption at temperatures above 300 K. For Ir₁₅, we begin to see ammonia production, signaling the onset of a transition to clusters able to support more complex chemistry.     

Band bending at the Si(1 1 1)–SiO2 interface induced by low-energy ion bombardment

Experiments employing photoreflectance spectroscopy have uncovered band bending due to electrically active defects at the Si(1 1 1)–SiO₂ interface after sub-keV Ar⁺ ion bombardment. The band bending of about 0.5 eV resembles that for Si(1 0 0)–SiO₂, and both interfaces exhibit two kinetic regimes for the evolution of band bending upon annealing due to defects healing. The healing takes place about an order of magnitude more quickly at the (1 1 1) interface, however, probably because of less fully saturated bonding and higher compressive stress.